Textile softening agents and method of applying them



United States Patent TEXTILE SOFTENING AGENTS AND METHOD OF APPLYING THEM Erich Matter, Riehen, Otto Albrecht, Neue-Welt, and Armin Hiestand, Binningen, Switzerland, assignors t Ciha Limited, Basel, Switzerland No Drawing. Filed Jan. 20, 1959, Ser. No. 787,832

Claims priority, application Switzerland Jan. 14, 1957 10 Claims. (Cl. 117-1395) The present invention is a continuation-in-part of our application Serial No. 706,281, filed December 31, 1957 (abandoned since the filing of the present application), and relates to new textile softening agents and a method of applying them.

According to the present invention a soft handle and feel can be imparted to textile material by contacting the material with an aqueous bath containing a di-quaternary ammonium compound of the general formula in which R and R each represents high molecular aliphatic hydrocarbon radicals, especially an alkyl radical having from 10 to 18 carbon atoms, R R R and R represent the same or different aliphatic, cycloaliphatic araliphatic or aromatic radicals, in which R and R and/0r R and R may together constitute a divalent Ialiphatic radical, R and R represent alkylene radicals, R represents a divalent aliphatic or aromatic radical,

R and R 'represent a hydrogen atom or a low molecular aliphatic radical, and X represents an anion.

As the radicals R R R and R there come into consideration, more especially, low molecular alkyland hydroxyalkyl groups, also high molecular aliphatic hydrocarbon radicals, as, for example, alkyl radicals having from 10 to 18 carbon atoms.

The invention is concerned, more especially, with compounds of the general symmetrical formula "ice in which R and R represent straight-chain alkyl group containing 10 to 18 carbon atoms, R each represents an aliphatic radical containing 1 to4 carbon atoms, and m and n represent small whole numbers.

Among these compounds there are preferred those in which m in the above formula is 1, 2 or 3, especially 1, and n is 1 The compounds can be obtained by known methods. For instance 2 mols of a compound of the formula R2\ R17N s may be quaternised with 1 mol of a compound of the formula in which X represents a substituent capable of forming an anion, especially a halogen atom.

As tertiary amines of the Formula 1 there may be mentioned, for example, dimethyl-dodecyl amine, dimethyloetylamine, dimethyl-octadecyl amine, diethyl-dodecyl amine, dipropyl-dodecyl amine, dibutyl-dodecyl amine, di-hydroxyethyl dodecyl amine, NzN-dimethyl-para-dodecyl aniline, didodecyl-methyl amine, dicetyl-methyl amine and dioctadecyl-methyl amine.

The diamides of the Formula 2 may themselves be prepared by the condensation of 1 mol of :a diprimary dior poly-amine of the formula H N-R --NH with 2 mols of a halogeno-fatty acid, or a functional derivative thereof, for example, chloracetic acid or chloracetic acid methyl ester.

The diamides of the Formula 2 in which R represents a radical (in which R represents H, CH or -'C H are obtained by the condensation of 2 mols of an N-methylolamide of the formula or by means of a catalytic reaction of an aldehyde such as formaldehyde, acetaldehyde or benzaldehyde with acrylonitrile (or its homologues), hydrochloric acid and steam in the gaseous phase.

According to a further process 2 mols of a compound of the formula may be condensed with a compound of the formula Ha1R4'CNHR -NHCR4Hal ll ll (2) with splitting oif of hydrogen halide and the condensation product so obtained is then treated with a quaternating agent of the formula R X. As such quaternating or a functional derivative thereof, such as acid anhydride, acid ester or acid halide, may be condensed with 1 mol of a diprimary dior poly-amine of the formula Formula 4 can themselves be obtained by quaternating a tertiary amine of the formula or a functional derivative of such a carboxylic acid, with a diprimary dior poly-amine, and then treat the di-tertiary amine so obtained with 2 mols of a quaternating agent of the formula R X. As such quaternating agents there may be mentioned, for example, dodecyl bromide and octadecyl bromide.

Instead of the amines of Formula 5 there may be used those of the formula or a functional derivative thereof, and with the use of a quaternating agent of the formula R X.

As such quaternating agents there may be mentioned, for example, dimethyl sulfate, ethyl bromide, ethyl iodide and benzyl chloride.

According to a further method 2 mols of a diamine of the formula \NR4NH2 (7) R.

may be condensed with 1 mol of a dicarboxylic acid of the formula HOOOR COOH or a functional derivative thereof, such as acid anhydride, ester or acid halide, and the di-tertiary amine so obtained is treated with 2 mols of a quaternating agent of the formula R X.

As diamines of the Formula 7 there may be mentioned, for example, NzN-dimethyl ethylene diamine, NzN-dimethyl propylene diamine and NzN-diethyl ethylene diamine.

As dicarboxylic acids there come into consideration malonic acid, glutaric acid, adipic acid, maleic acid,

fumaric acid, butadie'ne-lz4-dicarboxy1ic acid, terephthalic acid, 1:4-naphthalene dicarboxylic acid and especially succinic acid, or their esters or acid halides.

Instead of diamine of the Formula 7 there may be used one of the formula and as quaternating agent one of the formula R X.

The following examples illustrate the invention, the parts being by weight:

Example 1 Polyacrylonitrile yarn (Orlon yarn type 42) was treated at 30 C. for half an hour and at a goods-toliquor ratio of 1:30, with a solution which contained 0.08% of the product described below calculated on the weight of the fibrous material. The yarn so treated possessed a very soft handle; which even after washing with a synthetic washing agent at 40 C. was only slightly impaired.

The product used in this example may be prepared as follows:

43 grams of dimethyl-dodecyl amine and 21.2 grams of a compound which had been obtained by condensation in the molecular ratio of 2:1 of chloracetic acid methyl ester with ethylene-diamine, were stirred for 5 hours at C.

There was obtained a light paste which was stirred with 400 ccs. of water-free ether. After suction-filtering in the cold there was obtained a colorless, wax-like mass. This product, which corresponds to the formula was a clear, water-soluble compound which was stable to sodium carbonate.

The quaternating reaction may also be carried out in aqueous solution. In this case the mixture was more easily stirrable.

' Example 2 The process described in Example 1 was carried out but with the use of a polyamide fiber, for example, nylon yarn. The textile material so treated possessed a very soft handle.

In a similar manner cotton yarn may also be treated.

Example 3 in which R represents the alkyl radical derived from hydrogenated tall oil fatty acid, and 5.3 gramsof N:N'- methylene-bis-(chloracetamide) of the formula was stirred for 6 hours on a boiling water bath while passing nitrogen through the apparatus. The di-quaternary ammonium salt so obtained, which corresponded to the formula O\ CH: /R $9 in which R represents the alkyl radical derived from coconut oil fatty acid (molecular weight 436), were mixed with 21.3 grams (0.1 mol) of a compound which was obtained by the condensation of 2 mols of chloracetic acid methyl ester with 1 mol of ethylene diamine, and the mixture was boiled under reflux in the presence of 200 ccs. of ethanol for 8 hours. After this time a test portion was dispersible in water. Thereupon 8 grams (0.2 mol) of powdered caustic soda were added and the alcoholic solution was concentrated in a vacuum produced by a good water vacuum pump while passing through nitrogen until the product was completely freed from alcohol. To the warm melt at 60 C. 25.2 grams (0.2 mol) of neutral dimethyl sulfate were added. There was obtained a wax-like reaction product of the formula R 63$ N-OH -C-NELOHrCHr-NILO-OHrN :l2CHaOSOa R Ii R lHa O O Cs which was dispersible in hot water. After rubbing it with about 5 times its weight of alcohol the product was soluble in water to a colloidal solution.

Example 5 .zor

in which R R R and R each represents an aliphatic hydrocarbon radical, containing from to 18 carbon atoms, R and R each represents a lower aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms, R R and R each represents an alkylene radical, and X represents the anion of a water-soluble inorganic acid.

2. The di-quaternary ammonium compound which corresponds to the formula in which R and R each represents a straight-chain alkyl radical containing from 10 to 18 carbon atoms, R represents an alkyl radical containing from 1 to 4 carbon atoms, m and n are small whole numbers and X repre sents the anion of a water-soluble inorganic acid.

3. The di-quaternary ammonium compoud which corresponds to the formula in which R and R each represents a straight-chain alkyl radical containing from 10 to 18 carbon atoms, R represents an alkyl radical containing from 1 to 4 carbon atoms, In and n are small whole numbers and X represents the anion of a water-soluble inorganic acid.

4. The compound of the formula R\(I3Ha H or? /R ease N-CHr-O-NH-OHz-NH-C-CHrN 201 R R wherein R represents the alkyl radical derived from hydrogenated tall oil fatty acid.

5. The compound of the formula R\CHa (I) CH3 /R G36) wherein R represents the alkyl radical derived from coconut oil fatty acid.

6. A process for imparting a soft handle and feeling to textile material which comprises impregnating the material in an aqueous bath containing the di-quaternary ammonium compound which corresponds to the general symmetrical formula in which R represents an aliphatic hydrocarbon radical containing from 10 to 18 carbon atoms, R and R each represents an aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms, R; and R each represents an alkylene radical, and X represents the anion of a water-soluble inorganic acid.

7. A process for imparting a soft handle and feeling to textile material which comprises impregnating the material in an aqueous bath containing the di-quaternary ammonium compound which corresponds to the formula in which R; and R each represents a straight-chain alkyl radical containing from 10 to 18 carbon atoms, R represents an alkyl radical containing from 1 to 4 carbon 7 atoms, m and n are small whole numbers and X represents the anion of a water-soluble inorganic acid.

8. A process for. imparting a soft handle and feeling to textile material which comprises impregnating the material in an aqueous bath containing the compound of the formula wherein R represents the alkyl radical derived from hydrogenated tall oil fatty acid.

9. A process for imparting a soft handle and feeling to textile material which comprises impregnating the material in an aqueous bath containing the compound of the formula wherein R represents the alkyl radical derived from coconut oil fatty acid.

10. A process for imparting a soft handle and feeling to textile material which comprises impregnating the material in an aqueous bath containing the compound of the formula CH3 CH3 References Cited in the file of this patent UNITED STATES PATENTS 2,176,896 Epstein et a1 Oct. 24, 1939 2,216,406 Austin Oct. 1, 1940 2,310,873 Sauer Feb. 9, 1943 2,334,709" Katzman et a1. 'Nov. 23, 1943 2,371,104 Kienle et a1 Mar. 6, 1945 2,569,409 De Benneville et a1 Sept. 25, 1951 2,653,898 Castillo et al. Sept. 29, 1953 2,669,582 Cusic Feb. 16, 1954 2,765,337 De Benneville et al. Oct. 2, 1956 2,832,799 Payne et al Apr. 29, 1958 FOREIGN PATENTS 210,482 Switzerland July 15, 1940 748,543 Germany Nov. 17, 1944 1,110,724 France Oct. 19, 1955 936,395 Germany Dec. 15, 1955 OTHER REFERENCES Phillips: Jour. Am. Chem. Soc., vol. 73, pages 5822+ 5824.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 9 5 7 May l6 1961 Erich Matter et al It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 5, lines 65 and 66 the lower left hand portion of the formula should appear as shown below instead of as in the patent:

column 6 lines 18 to 25 and lines 65 to 72,, the closing bracket, each occurrence, should appear as shown below instead of as in the patent: I

column 7 lines 8 and .28 after the closing bracket for "C12 each occurrence, read 2C1 0 Signed and sealed this 31st day of October 19610 (SEAL) Attest:

A ID L, LADD ERNEST W0 SWIDER D V Attesting Officer Commissioner of Patents 

6. A PROCESS FOR IMPARTING A SOFT HANDLE AND FEELING TO TEXTILE MATERIAL WHICH COMPRISES IMPREGNATING THE MATERIAL IN AN AQUEOUS BATH CONTAINING THE DI-QUATERNARY AMMONIUM COMPOUND WHICH CORRESPONDS TO THE GENERAL SYMMETRICAL FORMULA 